Process for the dyeing or printing of nitrogen containing textile materials

ABSTRACT

Process for dyeing or printing nitrogen containing native or synthetic fibrous materials, such as wool, silk or fibres of polyamide, which comprises the dyeing or printing of the said fibrous materials with a water-soluble dyestuff of the formula   IN WHICH F represents the rest of a monoazo- or 1-amino-4phenyl-amino-anthraquinone-2-sulfonic acid dyestuff, Y represents a direct linkage or one of the groups   OR   Z represents a hydrogen atom or an alkali metal atom or the ammonium group, and n represents the integer 1, 2 or 3, at a temperature between about 20* and about 115* C and at a pH-value between about 4.0 and about 7.5, the dyeings and prints so prepared being distinguished by very good fastness to processing and fastness to wear, such as fastness to wet and fastness to light.

United States Patent [1 1 [451 Sept. 23, 1975 Meininger et al.

[ PROCESS FOR THE DYEING OR PRINTING OF NITROGEN CONTAINING TEXTILE MATERIALS [75] Inventors: Fritz Meininger, Frankfurt (Main);

Klaus Hunger, Kelkheim, Fritz Osterloh, Bad Soden, Klaus Berner, Hofheim, all of Germany [73] Assignee: I-Ioechst Aktiengesellschaft,

Frankfurt (Main), Germany [22] Filed: Oct. 11, 1973 [211 Appl. No.: 405,427

[30] Foreign Application Priority Data Primary Examiner.loseph L. Schofer Assistant ExaminerA. L. Clingman Attorney, Agennor Firm-Curtis, Morris & Safford {57 ABSTRACT Process for dyeing or printing nitrogen containing native or synthetic fibrous materials, such as wool, silk or fibres of polyamide, which comprises the dyeing or printing of the said fibrous materials with a watersoluble dyestuff of the formula in which F represents the rest of a monoazoor lamino-4-phenyl-amino-anthraquinone-Z-sulfonic acid dyestuff, Y represents a direct linkage or one of the groups Or I ail (y).

Z represents a hydrogen atom or an alkali metal atom or the ammonium group, and n represents the integer 1, 2 or 3, at a temperature between about 20 and about 115 C and at a pl-l-value between about 4.0 and about 7.5, the dyeings andprints so prepared being distinguished by very good fastness to processing and fastness to wear, such as fastness to wet and fastness to light.

5 Claims, N0 Drawings PROCESS FOR THE DYEING OR PRINTING OF NITROGEN CONTAINING TEXTILE MATERIALS The present invention relates to a process for the dyeing or printing of nitrogen containing native or synthetic fibrous materials.

It has been found that fast dyeing or prints can be produced on nitrogen containing native or synthetic fibrous materials, such as wool, silk, polyamide or polyurethane fiber materials, by dyeing or printing the said fibrous materials with water-soluble dyestuffs of the general formula 1) CH C002 H 7- CCOZ in which F stands for the rest of a monoazo or l-amino- 4-phenyl-aminoanthraquinone2-sulfonic acid dyestuff, Y for a direct linkage or for one of the groups and :Efl

Z stands for a hydrogen atom or an alkali metal atom or for the ammonium group, and n stands for the inte ger of l, 2 or 3, at temperatures of from about 20 to about 115 C, preferably from about 40 C to about 110 C, and at pH-values of from about 4.0 to about 7.5.

The dyestuff rest F may be rests of monazo dyestuffs containing, as coupling component, for example, the rests of naphthols, naphthol sulfonic acids, naphthol carboxylic acid amides, pyrazolones or aceto-acetic acid arylamides. The monoazo dyestuff rests may con tain, as diazo components, amines of the benzene or naphthalene series which, likewise as the coupling components, may carry hydroxy, amino, alkyl, alkoxy, phenyl, acetylamino, benzoylamino and/or N-phenylcarbonamido groups and/or halogen atoms, such as chlorine or bromine atoms, all linked to the aromatic nucleus.

The dyeings are produced, for example either by directly dyeing from a dyebath containing inorganic salts, where required, for example alkali metal chlorides or sulfates, at the above indicated temperatures and pH- values. The dyebath may also contain auxiliary agents, for example levelling agents.

Dyestuffs of most closely related constitution that contain a grouping of the formula SO -CH --CH- -X instead of the grouping of the following formula (2), in which X stands for an organic or inorganic rest capable of being split off as an anion, except for the imino-diacetic acid, require an alkaline preand/or after-treatment for the production of a dyeing which is fast to 'wet processing on one of the aforementioned nitrogen containing fibrous materials.

. i The dyestuffs used are prepared from dyestuff com- -CH X, X representing an organic or inorganic rest capable of being split off as an anion, for example the acetoxy, phenoxy, methyl-sulfonyloxy or, preferably, the sulfatoxy or chlorine radical, except for the radical of imino-diacetic acid, by reacting these compounds with aminodiacetic acid in an aqueous medium in the presence of alkaline compounds, for example alkali metal hydroxides, carbonates or bicarbonates, at to 100 C, preferably at to 60 C. After the pI-I-value has been adjusted to 5 7 or a strong acid has been added, the desired dyestuffs of the above-cited general so cu -CH2 I I COOZ in which Z stands either for a hydrogen atom, a sodium or potassium atom or the ammonium group, depending on the pH-values chosen and the alkaline compound used, are obtained.

The dyestuffs are prepared from the dyestuff components containing the rest of the formula (2) according to the methods known per se, for example by azo coupling or by halogenoanthraquinone condensation. The novel dyestuffs may contain one to three groupings of the formula (2) per molecule.

The dyestuffs used according to the invention are distinguished, in comparison to the dyestuffs of the mentioned type having a similar structure, in that they do not require an alkaline preor after-treatment for the dyeing of nitrogen containing fibrous materials.

Used on the cited nitrogen containing fibrous materials, the novel dyestuffs used according to the invention afford valuable bright dyeings and prints which are distinguished by very good fastness to processing, such as fastness to fulling and pleating, and very good general fastness properties, such as fastness to wet processing, for example to washing, wetting and perspiration, as well as very good fastness to light. When the fastness to wet processing is being tested by extracting the dyed fibrous material with an aqueous pyridine solution, no decrease in color intensity is observed.

The present simplified dyeing and printing process is a substantial improvement in the dyeing method disclosed in German Pat. Nos. 965,902 and 966,651.

The following Examples serve to illustrate the inven tion, the parts and percentages being by weight unless stated otherwise.

EXAMPLE 1 Parts of a woollen fabric were treated for some minutes at 40 C in 5000 parts by volume of an aqueous liquor containing 1 part of the dyestuff of the formula to the boil for 15 minutes and dyeing was continued for R cu -CO0H 2 N SO -CH -CH -N\ v CH -COOK H0 8 and 10 parts of an anhydrous sodium sulfate, the pH- at 98C in 5000 parts by volume of an aqueous liquor value of the liquor being adjusted to 5 by means of containing 1 part of the dyestuff of the formula HOOC-H C R-H2CH2CO2S-N==n v HOOC-H C HO CO-NHQ acetic acid The liquor was heated to 70 C within and the pl-l-value of which was adjusted to 6 by means minutes, the fabric was dyed for 15 minutes at this temf acetic id, The dyeing obtained had a reddish p the bath vlasiagain heated to C for 15 orangeshade and very good fastness properties to wet minutes, dyeing was continued for 15 minutes at this processing temperature, the temperature of the bath was brought EXAMPLE 4 half an hour a this mper ure- A rig y y g 100 Parts of natural silk weretreated at 20 C in 5000 Y 6%), 2 parts of acetic acid (of strength), 20 parts H c-oc4m on having y good vfastness to wet Processing was parts by volumeof an aqueous liquor containing 1 part tained. of the dyestuff of the formula I I I 1 Y H 11 HOOO-H .c

R -H C-H2C-O S@ ==N nooc-n c y EXAMPLE 2 A woollen fabric was printed with aprinting paste containing, per 1000 parts, 400 parts of crystal gum (of and the 'pl-l-value of which had been adjustedto 5.5 by .means of formic acid. The dyebath was heated to the boil and the goods-were dyed for- 1 hour at boiling temperature. A red dyeing having very good fastness to wet of the sodium salt of m-nitro-benzene-sulfonic acid and r I processing was obtained.

20 parts of the dyestuff of the formula the paste having been standardized with 558 parts of A v I 7 EXA 5 w water or crystal gum (6%) to avolume of 1000 parts. A polyamide fabri was printed with?! printing paste The print was then dried and steamed'for 30 minutes ntaining, P r 000 parts,' o parts f crystal gum at a pressure of 0.5 atmosphere gauge. A bluishred (6%), 1 part of acetic. acid (30%), 1 0 partsof the soprint having very good fastness to wet processing was diu'm salt of rn-nitro-benzene-sulfonic acid and 2O parts obtained. 7 v I I "of the dyestuff of the formula ow- 1p EXAMPLE 3 the paste having been standardized with 569 parts of water or erystal gum (6%) to a volume of 1000 parts. Parts of a polyamide fabric were dyed for 1 h The print was driedand steamed for 30 minutes at a pressure of O- to 5 atmospheres gauge. A yellow print having very good fastness to wet processing was obtained.

EXAMPLE 6 "HA C SOH and the pH-value of which was adjusted to 5. A brilliant blue dyeing having very good fastness to wet processing 25 was obtained.

EXAMPLE 7 c ooH -COOHg CIl -COOH GH -CODE was used instead of the dyestuff used in Example 6 and the dyeing operation was carried out as in Example 6, a somewhat more greenish brilliant blue dyeing was obtained on the woollen yarn.

The following Table comprises further dyestuffs to be used according to the invention as well as the shades obtainable with these dyestuffs upon the dyeing of When 1 part of the dyestuff of the formula 30 WODL T A B No. dyestuff Shade on wool red 8 .33 (3H H0OC-CH -N-CH -COOH I on' g i I I 9 8.0 H orange H0OC-CH -N-CH COOH 0911 on 1m-co CH 7 10 red 4 T A B L E (continued) No. dyestuff I Shade on wool Br H? N=N 11 302 11 yollowid: rod

HOOC-CH -N--CH COOH 0 S0 11 011 -000! so -01! 4m '-1r I but.

I I Gi -coon O Il-I OCH 40 We claim: Z represents a hydrogen or alkali metal atom or the am- I. Process for dyeing or printing nitrogen'containing native or synthetic fibrous materials, which comprises the dyeing or printing of the said fibrous materials with a water-soluble dyestuff of the formula v CH 'COOZ CH CD02 in which F represents the rest of a monoazo-or l amino-4-phenyl-amino-anthraquinone-Z-sulfonic acid dyes'tuff, Y represents a direct linkage or one of the groups printing is carried out at a temperature between about 40 and about 1 10 C.

3. Process as claimed in claim 1, wherein dyeing is a carried out according to the exhaust process.

4. Process as claimed in claim 1, wherein the dyestuff is applied to the fibrous materials by a printing process and the dyestuff is subsequently fixed by steaming at about 1 15 C.

carried out under pressure at C. 

1. A PROCESS FOR DYEING OR PRINTING NITROGEN CONTAINING NATIVE OR SYNTHETIC FIBROUS MATERIALS, WHICH COMPRISES THE DYEING OF PRINTING OF THE SAID FABROUS MATERIALS WITH A WATER-SOLUBLE DYESTUFF OF THE FORMULA
 2. Process as claimed in claim 1, wherein dyeing or printing is carried out at a temperature between about 40* and about 110* C.
 3. Process as claimed in claim 1, wherein dyeing is carried out according to the exhaust process.
 4. Process as claimed in claim 1, wherein the dyestuff is applied to the fibrous materials by a printing process and the dyestuff is subsequently fixed by steaming at about 115* C.
 5. Process as claimed in claim 1, wherein dyeing is carried out under pressure at 105* C. 